JP2005104025A - Laminated film with gas barrier properties and image display element using this laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated film with gas barrier properties which shows high flexing resistance/heat resistance and high gas barrier performance, and an image display element which uses the laminated film with gas barrier properties as a substrate and shows high definition/durability. <P>SOLUTION: This laminated film with gas barrier properties has at least one inorganic layer and one layer of polysilsesquioxane (a defect compensating layer), laminated on a base material film. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a laminated film having excellent heat resistance, durability, and gas barrier properties, and an image display such as an organic electroluminescence element (hereinafter referred to as “organic EL element”) or a liquid crystal display element using the laminated film as a substrate. It relates to an element. In particular, the present invention relates to a gas barrier laminate film substrate and an image display element using a flexible support.

  With the spread of personal computers and portable information terminals, the demand for light and thin electronic displays is increasing rapidly. At present, a glass substrate is mainly used as the substrate of the most popular liquid crystal display element and the organic EL element which has recently attracted attention because of its high visibility due to self-coloring. From the viewpoints of weight reduction of the element, durability against impact, flexibility, and the like, it is preferable to use a flexible plastic substrate as the substrate in the liquid crystal surface element or the organic EL element. However, since the plastic substrate is inferior in heat resistance and gas barrier property as compared with the glass substrate, it is unsuitable for producing a high-definition pattern and further has a drawback that it lacks durability.

  Many studies have been reported so far to improve such defects in plastic substrates. For example, the following patent documents have been reported as techniques for improving gas barrier properties (see Patent Documents 1 to 6).

  Patent Document 1 discloses an example in which a multilayer plastic substrate having a layer containing a layered compound is used for a liquid crystal display device. Patent Document 1 describes that heat resistance, hardness, and air resistance can be improved by using a layered compound. However, the gas barrier properties are not sufficient, and further improvements are required.

  Patent Document 2 discloses a laminated film in which a composition layer composed of a layered inorganic compound having a specific aspect ratio and a resin is provided between polyolefin resin layers in order to achieve both moisture resistance and oxygen barrier properties. Further, Patent Document 3 discloses a film having a gas barrier layer made of a mixture of a partially hydrolyzed polycondensate of alkoxide and a water-soluble polymer. However, none of these films have sufficient oxygen barrier properties under high humidity, and the gas barrier properties of laminated films have been further improved for use in crystal display substrates and organic EL substrates used under high temperature conditions. There was a need to do.

  On the other hand, Patent Document 4 discloses a substrate for an organic EL element in which a polymer layer and an inorganic layer are combined. However, the adhesion between the polymer layer and the inorganic layer of this substrate was not satisfactory. Furthermore, the polymer layer of this substrate does not have sufficient heat resistance due to the difference in coefficient of linear expansion from the adjacent layer required when installing TFTs during the production of active matrix image elements, and further improvement is required. there were.

  Further, Patent Document 5 discloses a gas barrier laminate film in which an organic-inorganic hybrid polymer layer and an inorganic layer are combined. However, the level of gas barrier properties of this film is not sufficient, and further improvement has been desired.

Furthermore, Patent Document 6 discloses a gas barrier laminate film in which organic layers and inorganic layers are alternately laminated. However, although this film can improve the flexibility to some extent, the heat resistance of the organic layer is insufficient, and further improvement has been desired.
JP 2001-205743 A (page 3 [0012] to page 10 [0062]) JP 7-251489 A (3rd page [0005] to 8th page [0034]) JP 2000-343659 A (2nd page [0010] to 7th page [0058]) US Pat. No. 6,268,695 (4th page [2-5] to 5th page [4-49]) JP 2002-301793 (page 4 [0010] to page 13 [0126]) JP 2003-53881 A (page 3 [0006] to page 4 [0008])

  The present invention has been made in view of the above problems, and a first object of the present invention is to provide a gas barrier laminate film having excellent durability, heat resistance and gas barrier properties. A second object of the present invention is to provide an image display element having high definition and high durability using the gas barrier laminate film.

  The inventor diligently studied the development of a film having excellent flex resistance and heat resistance and high gas barrier performance. As a result, the use of polysilsesquioxane succeeded in the development of a gas barrier film satisfying all of bending resistance, heat resistance and gas barrier properties, thereby completing the present invention.

  That is, the first object of the present invention is achieved by a gas barrier laminate film having at least one inorganic layer and at least one layer containing polysilsesquioxane on the base film.

  The gas barrier laminate film of the present invention preferably has the inorganic layer and a layer containing polysilsesquioxane on the base film in this order.

  Furthermore, in the gas barrier laminate film of the present invention, the polysilsesquioxane is preferably a cage polysilsesquioxane or a partial cleavage structure thereof.

  Furthermore, in the gas barrier laminate film of the present invention, the layer containing polysilsesquioxane is preferably a layer containing a copolymer of polysilsesquioxane having a polymerizable functional group and a polyfunctional monomer. .

  Furthermore, in the gas barrier laminate film of the present invention, the base film preferably contains an inorganic layered compound.

Furthermore, the gas barrier laminate film of the present invention has an oxygen transmission rate of 0.01 ml / m ² · day · atm or less at 38 ° C. and a relative humidity of 90%, and has a water vapor transmission rate of 38 ° C. and a relative humidity of 90%. It is preferably 0.01 g / m ² · day or less.

  The second object of the present invention is achieved by an image display device using the gas barrier laminate film as a substrate.

  In the present invention, a layer containing polysilsesquioxane (herein also referred to as a defect filling layer) is laminated on an inorganic thin film layer. With this configuration, it is possible to obtain a gas barrier laminate film having high gas barrier performance, particularly excellent bending resistance and heat resistance.

  Furthermore, since the image display element of the present invention has the gas barrier laminate film of the present invention, if it is the present invention, an image of a liquid crystal display device having high definition and high durability using a flexible support, an organic EL element, etc. A display element can be provided.

  The gas barrier laminate film of the present invention and an image display device using the film will be described in detail below.

[Gas barrier laminate film]
The gas barrier laminate film of the present invention has at least one inorganic layer and at least one layer containing polysilsesquioxane on the base film. That is, the gas barrier laminate film of the present invention is applied with a layer containing polysilsesquioxane (defect filling layer), so as to compensate for “defects” present in the inorganic layer, and at the same time, heat resistant to the gas barrier film. Flexibility and gas barrier properties can be imparted.
In addition, in this specification, the laminated body which consists of an inorganic layer and the layer (defect filling layer) containing polysilsesquioxane is also called "gas barrier coating layer."

<Layer containing polysilsesquioxane>
In the gas barrier laminate film of the present invention, it is a layer containing polysilsesquioxane as a main component and has an effect of compensating for defects, and is also referred to as a defect compensation layer here.

(Polysilsesquioxane)
The polysilsesquioxane used in the present invention will be described. Polysilsesquioxane is a compound containing silsesquioxane in a structural unit. The “silsesquioxane” is a compound represented by [RSiO _3/2 ], and is usually RSiX ₃ (R is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an araalkyl group, etc. Is a polysiloxane synthesized by hydrolysis-polycondensation of a type compound (such as a halogen or an alkoxy group). The shape of the molecular arrangement of cissesoxane is typically an amorphous structure, a ladder structure, a cage structure or a partially cleaved structure thereof (a structure in which one silicon atom is missing from the cage structure or a part of the cage structure) A structure in which a silicon-oxygen bond is broken is known. In the case of polysilsesquioxane having an amorphous structure and a ladder-like structure, it exists in the defect filling layer in the form of a polymer with silsesquioxane as a monomer unit. Further, in the case of a polysilsesquioxane having a cage structure or a partial cleavage structure thereof, the polysilsesquioxane is present in the defect filling layer in a form including a plurality of silsesquioxanes having one structure.
In the present invention, among the silsesquioxanes, a cage polysilsesquioxane and a partial cleavage structure thereof can be preferably used.

Examples of the cage silsesquioxane include silsesquioxane of the following general formula (1) represented by the chemical formula of [RSiO _3/2 ] _{8 and} the following formula represented by the chemical formula of [RSiO _3/2 ] ₁₀ Silsesquioxane of general formula (2), represented by chemical formula of [RSiO _3/2 ] ₁₂ Silsesquioxane of general formula (3), represented by chemical formula of [RSiO _3/2 ] ₁₄ Examples thereof include silsesquioxane of the general formula (4) and silsesquioxane of the following general formula (5) represented by a chemical formula of [RSiO _3/2 ] ₁₆ .

The value of n in the cage silsesquioxane represented by [RSiO _3/2 ] _n is an integer of 6 to 20, preferably 8, 10 or 12, particularly preferably 8 or 8, 10 And 12 mixtures. In addition, [RSiO _3/2 ] _nm (O _1/2 H) _{2 + m} (n is an integer of 6 to 20) in which part of the silicon-oxygen bond of the cage silsesquioxane is partially cleaved. m is 0 or 1. As a preferable example of the cage silsesquioxane represented by the formula (1), a trisilanol compound in which a part of the general formula (1) is cleaved, [RSiO _3/2 ] ₇ (O _{1 / 2} H) ₃ silsesquioxane of the following general formula (6), silsesquioxane of the following general formula (7) represented by the chemical formula of [RSiO _3/2 ] ₈ (O _1/2 H) ₂ Oxane, silsesquioxane of the following general formula (8) represented by the chemical formula of [RSiO _3/2 ] ₈ (O _1/2 H) ₂ may be mentioned.

  R in the general formulas (1) to (8) is a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an araalkyl group having 7 to 20 carbon atoms, or 6 to 6 carbon atoms. There are 20 aryl groups. Among these, R is preferably a polymerizable functional group capable of polymerization reaction.

  Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, butyl group (n-butyl group, i-butyl group, t-butyl group, sec -Butyl group, etc.), pentyl group (n-pentyl group, i-pentyl group, neopentyl group, cyclopentyl group, etc.), hexyl group (n? Hexyl group, i-hexyl group, cyclohexyl group etc.), heptyl group (n- Heptyl group, i-heptyl group, etc.), octyl group (n-octyl group, i-octyl group, t-octyl group, etc.), nonyl group (n-nonyl group, i-nonyl group, etc.), decyl group (n- Decyl group, i-decyl group, etc.), undecyl group (n-undecyl group, i-undecyl group, etc.), dodecyl group (n-dodecyl group, i-dodecyl group, etc.) and the like. In consideration of the balance of melt fluidity, flame retardancy and operability during molding, it is preferably a saturated hydrocarbon having 1 to 16 carbon atoms, particularly preferably a saturated hydrocarbon having 1 to 12 carbon atoms.

  Examples of the alkenyl group having 2 to 20 carbon atoms include acyclic alkenyl groups and cyclic alkenyl groups. Examples thereof include vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group, cyclohexenylethyl group, norbornenylethyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, A dodecenyl group etc. are mentioned. In consideration of the balance of melt fluidity, flame retardancy and operability during molding, an alkenyl group having 2 to 16 carbon atoms is preferable, and an alkenyl group having 2 to 12 carbon atoms is particularly preferable.

  Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a phenethyl group, or a benzyl group, a phenethyl group, etc., which are substituted by 1 or more carbon atoms among alkyl groups having 1 to 13 carbon atoms, preferably 1 to 8 carbon atoms. Is mentioned.

  Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, or a phenyl group substituted with an alkyl group having 1 to 14 carbon atoms, preferably 1 to 8 carbon atoms, a tolyl group, and a xylyl group. It is done.

  As the above-mentioned cage silsesquioxanes, compounds commercially available from Aldrich, Hybrid Plastic, Chisso, Amax, etc. may be used as they are, and Journal of American Chemical Society, Vol. 111 1741 (1989), etc., may be used.

The partial cleavage structure of a polysilsesquioxane cage structure is a Si-O-Si bond generated by cleavage of a Si-O-Si bond from one cage unit represented by the chemical formula [RSiO _3/2 ] _8. A compound having 3 or less OH, or a compound having 1 or less Si atom deficiency in a closed cage structure represented by the chemical formula [RSiO _3/2 ] ₈ .

  The polysilsesquioxane is preferably used by mixing with a binder capable of reacting with the functional group R. Examples of the reactive binder include a thermosetting resin and a radiation curable resin.

Examples of the thermosetting resin include epoxy resins and radiation curable resins.
Examples of the epoxy resin include polyphenol type, bisphenol type, halogenated bisphenol type, and novolac type. A known curing agent can be used as the curing agent for curing the epoxy resin. Examples thereof include curing agents such as amines, polyaminoamides, acids and acid anhydrides, imidazoles, mercaptans, and phenol resins. Among them, from the viewpoint of solvent resistance, optical properties, thermal properties, etc., polymers containing acid anhydrides and acid anhydride structures or aliphatic amines are preferably used, and polymers containing acid anhydrides and acid anhydride structures are particularly preferred. Used. Furthermore, it is preferable to add an appropriate amount of a known curing catalyst such as tertiary amines and imidazoles.

  A radiation curable resin is a resin that cures when irradiated with radiation such as ultraviolet rays and electron beams. Specifically, it is an unsaturated double molecule such as an acryloyl group, a methacryloyl group, or a vinyl group in a molecule or a single structure. A resin containing a bond. Among these, an acrylic resin containing an acryloyl group is particularly preferable. The radiation curable resin may be one kind of resin or a mixture of several kinds of resins, but it is preferable to use an acrylic resin having two or more acryloyl groups in the molecule or unit structure. preferable. Examples of such polyfunctional acrylate resins include, but are not limited to, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, urethane acrylate, ester acrylate, epoxy acrylate, and the like.

  In the case of using an ultraviolet curing method, an appropriate amount of a known photoreaction initiator is added to these radiation curable resins.

  In the layer containing the silsesquioxane of the present invention (defect filling layer), the combination of the silsesquioxane and the binder is composed of a copolymer of a silsesquioxane having a polymerizable functional group and a polyfunctional monomer. A layer is preferred. The combination of the polymerizable functional group R of silsesquioxane and the copolymerizable binder is preferably such that R is an acryloyl group and the reactive binder is a polyfunctional acrylate. Also preferred is an embodiment in which R is an epoxy group and the reactive binder is a polyfunctional epoxy.

  In order to further enhance the interaction with silsesquioxane, the epoxy resin and the radiation curable resin may be mixed with a hydrolyzate of alkoxysilane or a silane coupling agent. As the silane coupling agent, one having a hydrolyzable reactive group such as a methoxy group, an ethoxy group, or an acetoxy group and the other having an epoxy group, a vinyl group, an amino group, a halogen group, or a mercapto group. preferable. In this case, it is particularly preferable to have a vinyl group having the same reactive group for fixing to the main component resin. For example, KBM-503 and KBM-803 of Shin-Etsu Chemical Co., Ltd., manufactured by Nippon Unicar Co., Ltd. A-187 or the like is used. These addition amounts are preferably 0.2 to 3% by mass.

  The content of polysilsesquioxane in the defect filling layer is suitably 50 to 100% by mass, and preferably 60 to 90% by mass. If the content of polysilsesquioxane is 50 to 100% by mass, a gas barrier laminate film having good heat resistance and gas barrier properties can be obtained.

  The thickness of the polysilsesquioxane-containing layer (defect filling layer) in the present invention is not particularly limited, but is preferably in the range of 10 nm to 5 μm, more preferably in the range of 10 nm to 2 μm, and 10 nm to More preferably, it is in the range of 0.5 μm. If the thickness of the defect filling layer is too thin, it will be difficult to obtain a uniform thickness. Therefore, structural defects in the inorganic layer cannot be efficiently filled with the defect filling layer, and no improvement in barrier properties is observed. . On the other hand, if the thickness of the defect compensation layer is too thick, the defect compensation layer is liable to crack due to an external force such as bending, which causes a problem that the barrier property is lowered.

  Examples of the method for forming the defect filling layer of the present invention include a coating method and a vacuum film forming method. Although there is no restriction | limiting in particular as a vacuum film-forming method, Film-forming methods, such as vapor deposition and plasma CVD, are preferable, and the resistance heating vapor deposition method which is easy to control the film-forming rate of an organic substance monomer is more preferable. The method of crosslinking the organic substance monomer of the present invention is not limited in any way, but crosslinking by electron beam or ultraviolet ray by irradiation of active energy rays is easy to attach in a vacuum chamber, and high molecular weight by crosslinking reaction is rapid. Is desirable.

  When the coating method is used, various conventionally used coating methods such as roll coating, gravure coating, knife coating, dip coating, curtain flow coating, spray coating, and bar coating can be used.

  The active energy ray means radiation capable of propagating energy by irradiation with ultraviolet rays, X-rays, electron beams, infrared rays, microwaves, and the like, and the type and energy thereof can be arbitrarily selected according to the application. .

<Inorganic layer>
In the present invention, the inorganic layer is preferably a layer made of a metal oxide such as silicon, aluminum, titanium, zirconium, or tin from the viewpoint of obtaining transparency. In addition, when transparency is not required or when two or more inorganic thin film layers are formed, the inorganic layer (if two or more layers, one of them) is formed of nitride, the above-mentioned metal alone or a composite thereof. May be.

  The inorganic layer can be formed by vapor deposition, physical vapor deposition (PVD) such as sputtering or ion plating, various chemical vapor deposition (CVD), or liquid phase such as plating or sol-gel. There is a growth method. Among these, chemical vapor deposition (CVD) and physical vapor deposition are effective in avoiding the effects of heat on the base film during inorganic layer formation, high production speed, and easy to obtain a uniform thin film layer. The method (PVD) is preferred. Moreover, it is also preferable to form an inorganic layer by a sol-gel method from the viewpoint that a thick film can be easily obtained. Here, the thick film refers to a film in the range of 100 nm to 1 μm.

  The thickness of the inorganic layer is preferably 30 nm to 1 μm, and more preferably 50 to 200 nm. When the thickness of the inorganic layer is in the range of 50 to 1 μm, it is difficult to be influenced by defective portions or portions having low density between crystals, and high gas barrier properties can be obtained. Further, even when it is deformed, the destruction of the inorganic layer can be reduced, which is preferable in practice.

Next, a method for coating an inorganic layer using a sol-gel method will be described.
<Metal alkoxide>
In the present invention, the metal alkoxide is used as an inorganic oxide component of the gas barrier coat layer. From the viewpoint of reactivity, the metal alkoxide is preferably alkoxysilane. In addition to alkoxysilane, it is also preferable to use zirconium alkoxide, titanium alkoxide, aluminum alkoxide, or the like. You may use a metal alkoxide individually or in mixture of 2 or more types of metal alkoxides.

The alkoxysilanes preferably used in the present invention will be further described.
Examples of alkoxysilanes include compounds represented by the following general formula.

R ² in the above formula is preferably an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, or an n-butyl group. , Sec-butyl group, tert-butyl group, acetyl group and the like. R ³ is preferably an organic group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, n-hexyl group, Unsubstituted hydrocarbon group such as cyclohexyl group, n-octyl group, tert-octyl group, n-decyl group, phenyl, vinyl group, allyl group, γ-chloropropyl group, CF ₃ CH ₂ —, CF ₃ CH _{2 CH 2 -, C 2 F 5} CH 2 CH 2 -, C 3 F 7 CH 2 CH 2 CH 2 -, CF 3 OCH 2 CH 2 CH 2 -, C 2 F 5 OCH 2 CH 2 CH 2 -, C 3 _{F 7 OCH 2 CH 2 CH 2} -, (CF 3) 2 CHOCH 2 CH 2 CH 2 -, C 4 F 9 CH 2 OCH 2 CH 2 CH 2 -, 3- ( perfluoro-cyclohexyl) propyl, (CF ₂ ) ₄ CH ₂ OCH ₂ CH ₂ CH _2- , H (CF ₂ ) ₄ CH ₂ CH ₂ C Examples thereof include substituted hydrocarbon groups such as H _2- , γ-glycidoxypropyl group, γ-mercaptopropyl group, 3,4-epoxycyclohexylethyl group, and γ-methacryloyloxypropyl group. x is preferably an integer of 2 to 4.

Specific examples of these alkoxysilanes are shown below.
Examples of x = 4 include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, and tetra-acetoxysilane.

As x = 3, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltrimethoxysilane, iso -Propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane , Γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxy _{Run, CF 3 CH 2 CH 2 Si} (OCH 3) 3, C 2 F 5 CH 2 CH 2 Si (OCH 3) 3, C 2 F 5 OCH 2 CH 2 CH 2 Si (OCH 3) 3, C 3 F ₇ OCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , (CF ₃ ) ₂ CHOCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₄ F ₉ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H (CF ₂ ) ₄ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , 3- (perfluorocyclohexyloxy) propyltrimethoxysilane, and the like.

As x = 2, dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di- iso- propyl dimethoxysilane, di -iso- propyl diethoxy silane, diphenyl dimethoxy silane, divinyl diethoxy _{silane, (CF 3 CH 2 CH 2} ) 2 Si (OCH 3) 2, (C 3 F 7 OCH 2 CH 2 CH ₂ ) ₂ Si (OCH ₃ ) ₂ , [H (CF ₂ ) ₆ CH ₂ OCH ₂ CH ₂ CH ₂ ] ₂ Si (OCH ₃ ) ₂ , (C ₂ F ₅ CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) ₂ etc. can be mentioned.

  A polymer may be used in combination during the sol-gel reaction. The polymer preferably has a hydrogen bond forming group. Examples of polymers having hydrogen bond-forming groups include polymers having hydroxyl groups and derivatives thereof (polyvinyl alcohol, polyvinyl acetal, ethylene-vinyl alcohol copolymers, phenol resins, methylol melamine, and derivatives thereof); Polymers and derivatives thereof (single or copolymer containing units of polymerizable unsaturated acid such as poly (meth) acrylic acid, maleic anhydride, itaconic acid, and esterified products of these polymers (vinyl esters such as vinyl acetate, Homo- or copolymers containing units such as (meth) acrylic acid esters such as methyl methacrylate)); polymers having an ether bond (polyalkylene oxide, polyoxyalkylene glycol, polyvinyl ether, silicon resin, etc.); amide bond (> N ( COR) -bond (wherein R represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent) N- of polyoxazoline or polyalkyleneimine Acylated compounds);> polyvinylpyrrolidone having a NC (O) -bond and derivatives thereof; polyurethane having a urethane bond; polymer having a urea bond, and the like.

  Below, the reaction conditions at the time of inorganic layer formation are demonstrated.

In the sol-gel reaction, the metal alkoxide is hydrolyzed and polycondensed in water and an organic solvent. In this case, it is preferable to use a catalyst. As a catalyst for hydrolysis, an acid is generally used. As the acid, an inorganic acid or an organic acid is used.
Inorganic acids include hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, etc., and organic acid compounds include carboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, succinic acid, Cyclohexanecarboxylic acid, octanoic acid, maleic acid, 2-chloropropionic acid, cyanoacetic acid, trifluoroacetic acid, perfluorooctanoic acid, benzoic acid, pentafluorobenzoic acid, phthalic acid, etc.), sulfonic acids (methanesulfonic acid, ethanesulfone) Acid, trifluoromethanesulfonic acid), p-toluenesulfonic acid, pentafluorobenzenesulfonic acid, etc.), phosphoric acid / phosphonic acids (phosphoric acid dimethyl ester, phenylphosphonic acid, etc.), Lewis acids (boron trifluoride etherate, scandium triflate, Alkyl titanic acid, aluminate, etc.), hetero It can be mentioned Li acid (phosphomolybdic acid, phosphotungstic acid).

  The amount of the acid used is 0.0001 to 0.05 mol, preferably 0.001 per mol of metal alkoxide (alkoxysilane and other metal alkoxide in the case of containing alkoxysilane + other metal alkoxide). -0.01 mol.

After hydrolysis, a basic compound such as an inorganic base or an amine may be added to bring the pH of the solution to near neutrality to promote condensation polymerization.
Examples of inorganic bases include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and ammonia. Examples of organic base compounds include amines (ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, triethylamine, Dibutylamine, N, N-dimethylbenzylamine, tetramethylethylenediamine, piperidine, piperazine, morpholine, ethanolamine, diazabicycloundecene, quinuclidine, aniline, pyridine, etc.), phosphines (triphenylphosphine, trimethylphosphine, etc.) Can be used.
It is also preferable to use an amine represented by the following general formula described in Japanese Patent Application No. 2002-110061 after hydrolysis with an acid.

In the general formula, R ¹ and R ² represent a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic sulfonyl group, and an aromatic sulfonyl group, and R ³ represents an aromatic group. An oxy group, an aliphatic thio group, an aromatic thio group, an acyloxy group, an aliphatic oxycarbonyloxy group, an aromatic oxycarbonyloxy group, a substituted amino group, a heterocyclic group, or a hydroxy group is represented. However, when R ³ is not an aromatic group, one or both of R ¹ and R ² are hydrogen atoms.
In this case, the addition amount of the amine is suitably equimolar to 100 times mol, preferably equimolar to 20 times mol with respect to the acid.

Other sol-gel catalysts can also be used in combination. Examples are given below.
(1) Metal chelate compound An alcohol represented by the general formula R ⁴ OH (wherein R ⁴ represents an alkyl group having 1 to 6 carbon atoms) and R ⁵ COCH ₂ COR ⁶ (where R ⁵ is carbon 1 to 6 alkyl groups, R ⁶ represents an alkyl group having 1 to 5 carbon atoms or a diketone represented by an alkoxy group having 1 to 16 carbon atoms) and a metal as a central metal. Any material can be suitably used without particular limitation. Within this category, two or more metal chelate compounds may be used in combination. Particularly preferred as the metal chelate compound of the present invention is one having Al, Ti, or Zr as the central metal, and has the general formula Zr (OR ⁴ ) _p1 (R ⁵ COCHCOR ⁶ ) _p2 , Ti (OR ⁴ ) _q1 (R ⁵ Those selected from the group of compounds represented by COCHCOR ⁶ ) _q2 and Al (OR ⁴ ) _r1 (R ⁵ COCHCOR ⁶ ) _r2 are preferred and serve to promote the condensation reaction.

R ⁴ and R ⁵ in the metal chelate compound may be the same or different, and an alkyl group having 1 to 6 carbon atoms, specifically, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group. , Sec-butyl group, tert-butyl group, n-pentyl group, phenyl group and the like. R ⁶ represents an alkyl group having 1 to 6 carbon atoms as described above, or an alkoxy group having 1 to 16 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, and n-butoxy. Group, sec-butoxy group, tert-butoxy group, lauryl group, stearyl group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be 4 or 6-coordinated.

  Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum. Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

(2) Organometallic compound Although there is no restriction | limiting in particular as a preferable organometallic compound, Since an organic transition metal has high activity, it is preferable. Of these, tin compounds are particularly preferred because of their good stability and activity. Specific examples of these compounds include (C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH═CHCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Carboxylic acid type organotin compounds such as Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH═CHCOOC ₄ H ₉ ) ₂ , Sn (OCOCC ₈ H ₁₇ ) ₂ ; (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₁₂ H ₂₅ ) ₂ ,

Such as mercaptide type or sulfide type organotin compounds such as (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO, or (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO And organic tin compounds such as reaction products of organotin oxide and ester compounds such as ethyl silicate dimethyl maleate, diethyl maleate and dioctyl phthalate.

(3) Metal salts As metal salts, alkali metal salts of organic acids (for example, sodium naphthenate, potassium naphthenate, sodium octanoate, sodium 2-ethylhexanoate, potassium laurate, etc.) are preferably used.

  Next, the solvent used for the sol-gel reaction will be described. The solvent uniformly mixes each component in the sol solution, and at the same time prepares the solid content of the composition of the present invention, so that it can be applied to various coating methods to improve the dispersion stability and storage stability of the composition. Is. These solvents are not particularly limited as long as they can fulfill the above purpose. Preferable examples of these solvents include water and organic solvents that are highly miscible with water.

  Examples include tetrahydrofuran, dimethoxyethane, formic acid, acetic acid, methyl acetate, alcohols (methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, tert-butyl alcohol), ethylene glycol, diethylene glycol, triethylene glycol, ethylene. Examples thereof include glycol monobutyl ether, ethylene glycol monoethyl ether acetate, acetone, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethyl sulfoxide.

For the purpose of adjusting the reaction rate of the sol-gel reaction, an organic compound capable of multidentate coordination may be added to stabilize the metal alkoxide. Examples thereof include β-diketones and / or β-ketoesters, and alkanolamines.
Specific examples of the β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-iso-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-sec-butyl, acetoacetic acid-tert-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane -Dione, 5-methyl-hexane-dione and the like can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketones and / or β-ketoesters may be used alone or in combination of two or more.
These compounds capable of multidentate coordination can also be used for the purpose of adjusting the reaction rate when the metal chelate compound is used as a sol-gel catalyst.

  The content of the polymer in the inorganic layer of the present invention is 3 to 97% by mass, preferably 5 to 65% by mass, based on the total solid content. The timing of addition of the polymer to the sol-gel reaction system is not particularly limited, but in terms of compatibility, it is preferably added before the beginning of the condensation reaction of the metal alkoxide, more preferably before the start of the sol-gel reaction, that is, It is preferable that the polymer and the metal alkoxide are mixed before addition of the acid catalyst.

  The reaction temperature and time during the formation of the inorganic layer are not particularly problematic as long as the reaction system is not heterogeneous. The combination of the materials used, the hydrolysis rate of the organic polymer during the formation of the target inorganic layer, and the metal alkoxide It can be appropriately adjusted according to the condensation rate.

  The inorganic layer produced by the sol-gel method produced by the above method can be applied by the following method. The sol liquid can form a thin film by a coating method such as curtain flow coating, dip coating, spin coating or roll coating. In this case, the hydrolysis may be performed at any time during the production process. For example, a solution of the required composition is hydrolyzed and partially condensed to prepare the desired sol solution, and this is applied and dried, and a solution of the required composition is prepared and dried while subjecting it to hydrolysis and partial condensation. Method, application-After primary drying, a method of applying a water-containing liquid necessary for hydrolysis repeatedly and applying hydrolysis can be suitably employed. In addition, the coating method can take various forms. However, when productivity is important, each of the lower layer coating solution and the upper layer coating solution is required on a slide Geyser having a multistage discharge port. A method (simultaneous multi-layer method) is preferably used in which the discharge flow rate is adjusted so that the coating amount is obtained, and the formed multilayer flow is continuously placed on a support and dried.

  The drying temperature after coating is not particularly limited as long as it does not cause deformation of the support, but is preferably 150 ° C. or lower, more preferably 30 to 150 ° C., and particularly preferably 50 to 130 ° C.

In order to make the film after coating and drying more dense, energy rays may be irradiated immediately after coating, during and / or after drying. Although there is no restriction | limiting in particular in the kind of irradiation radiation, In consideration of the influence with respect to a deformation | transformation and modification | denaturation of a support body, irradiation of an ultraviolet-ray, an electron beam, or a microwave can be used especially preferable. Of these, it is more preferable to use microwaves. The irradiation intensity is 30 to 500 mJ / cm ² , particularly preferably 50 to 400 mJ / cm ² . The irradiation temperature can be employed without limitation between room temperature and the deformation temperature of the support, and is preferably 30 to 150 ° C, particularly preferably 50 to 130 ° C.

  In the present invention, as described above, the coating method when forming the inorganic layer uses a coating method such as curtain flow coating, dip coating, spin coating, roll coating, etc., for the sol solution obtained by the sol-gel reaction. It can be performed by forming a thin film on the base film. In this case, the hydrolysis timing may be any time during the production process. For example, a solution of a required composition is hydrolyzed and partially condensed to prepare a desired sol solution, which is applied and dried, and a solution of the required composition is prepared and dried while hydrolyzing and partially condensing simultaneously. Method, application-After primary drying, a method of applying a water-containing liquid necessary for hydrolysis repeatedly and applying hydrolysis can be suitably employed.

<Base film>
The base film used in the gas barrier laminate film of the present invention is preferably made of a heat-resistant material so that it can be used as an image display element described later. Preferably, a transparent plastic film having a glass transition temperature (Tg) of 100 ° C. or higher and / or a linear thermal expansion coefficient of 40 ppm / ° C. or lower and high heat resistance is used as the base film. Tg and the linear expansion coefficient can be changed by an additive or the like.

The polymer used in the base film may be either a thermoplastic polymer or a thermosetting polymer.
The thermoplastic polymer preferably has a polymer Tg of 130 to 300 ° C, more preferably 160 to 250 ° C. Further, in order to achieve optical uniformity, an amorphous polymer is preferable. Examples of such thermoplastic resins include the following (in parentheses indicate Tg).

  Polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, ZEONOR 1600: 160 ° C. manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C.), polyethersulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: compound of Example 1 of JP 2001-150584 A: 162 ° C.), fluorene ring-modified polycarbonate (BCF-PC: Example 4 of JP 2000-227603 A) Compound: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound of Example 5 of JP 2000-227603 A: 205 ° C.), acryloyl compound (Example 1 of JP 2002-80616 A) Compound: 300 ° C. or higher). In particular, when moisture permeability is required, it is preferable to use an alicyclic polyolefin or the like.

Examples of the thermosetting polymer include epoxy resins and radiation curable resins.
Examples of the epoxy resin include polyphenol type, bisphenol type, halogenated bisphenol type, and novolac type. A known curing agent can be used as the curing agent for curing the epoxy resin. Examples thereof include curing agents such as amines, polyaminoamides, acids and acid anhydrides, imidazoles, mercaptans, and phenol resins. Among them, from the viewpoints of solvent resistance, optical properties, thermal properties, etc., polymers or aliphatic amines containing acid anhydrides and acid anhydride structures are preferably used, and particularly preferred are acid anhydrides and acid anhydride structures. It is a polymer containing. Furthermore, it is preferable to add an appropriate amount of a known curing catalyst such as tertiary amines and imidazoles.

  A radiation curable resin is a resin that cures when irradiated with radiation such as ultraviolet rays and electron beams. Specifically, it is an unsaturated double molecule such as an acryloyl group, a methacryloyl group, or a vinyl group in a molecule or a single structure. A resin containing a bond. Among these, an acrylic resin containing an acryloyl group is particularly preferable. The radiation curable resin may be one kind of resin or a mixture of several kinds of resins, but it is preferable to use an acrylic resin having two or more acryloyl groups in the molecule or unit structure. preferable. Examples of such polyfunctional acrylate resins include, but are not limited to, urethane acrylates, ester acrylates, epoxy acrylates, and the like. In particular, an acrylic resin containing units of the following formula [II] and / or [III] and having at least two acryloyl groups is preferable.

  In the case of using an ultraviolet curing method, an appropriate amount of a known photoreaction initiator is added to these radiation curable resins.

  In order to further strengthen the interaction with the polymer molecule, an alkoxysilane hydrolyzate or a silane coupling agent may be mixed with the epoxy resin and the radiation curable resin. As the silane coupling agent, one having a hydrolyzable reactive group such as a methoxy group, an ethoxy group, or an acetoxy group and the other having an epoxy group, a vinyl group, an amino group, a halogen group, or a mercapto group. Preferably, in this case, those having a vinyl group having the same reactive group are particularly preferably used for fixing to the main component resin. For example, KBM-503, KBM-803 of Shin-Etsu Chemical Co., Ltd., Nippon Unicar Co., Ltd. A-187 made by) or the like is used. These addition amounts are preferably 0.2 to 3% by mass.

  Since the gas barrier laminate film of the present invention is used as an image display element such as a display, it is a transparent substrate film, that is, a light transmittance of 80% or more, preferably 85% or more, more preferably 90% or more. It is preferable to use a substrate film that is If the light transmittance of the base film is 80% or more, it can be suitably used as a base film of an organic EL element described later.

  It goes without saying that an opaque material can be used for applications that do not necessarily require transparency, such as when not used on the viewing side even when used for display applications, or for opaque packaging materials. Examples thereof include polyimide, polyacrylonitrile, and known liquid crystal polymers.

  The light transmittance used as a scale of transparency in this specification is determined by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, using an integrating sphere light transmittance measuring device. It can be calculated by subtracting the diffuse transmittance from the light transmittance.

  The base film of the present invention can further contain an inorganic layered compound. It can be expected that the heat distortion temperature is improved by 2 to 100 ° C. by adding the inorganic layered compound to the base film. Further, it can be expected that the heat distortion temperature is improved by 10 ° C. or more as compared with the case where no inorganic layered compound is added.

The inorganic layered compound used in the laminated gas barrier film of the present invention is not particularly limited, but a clay mineral or hydrotalcite compound having a swellability and / or cleavage property and a similar compound are preferably used. Can do.
Examples of these clay minerals include kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectorite, tetrasilic mica, sodium. Examples include teniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite.

  The inorganic layered compound may be a natural product or a synthetic product. In addition, these layered silicates can be used alone or in combination.

  The shape of the inorganic layered compound is not particularly limited. However, if the inorganic layered compound is stacked in multiple layers, it is difficult to cleave after forming the organic layer. The thickness of the layered compound is preferably as thick as possible in one layer (about 1 nm). Further, those having an average length of 0.01 to 50 μm, preferably 0.05 to 10 μm, and an aspect ratio of 20 to 500, preferably 50 to 200 can be suitably used.

  The inorganic layered compound has an inorganic cation capable of ion exchange between its layers (including the surface of the uppermost or lowermost inorganic layered compound). The ion-exchangeable inorganic cation is a metal ion such as sodium, potassium or lithium existing on the crystal surface of the inorganic layered compound (for example, layered silicate). These ions have an ion exchange property with a cationic substance, and various substances having a cationic property can be intercalated between the layers of the inorganic layered compound by an ion exchange reaction.

  When an inorganic cation existing between the layers of the inorganic layered compound is ion-exchanged with an organic cation, an alkyl ammonium ion containing a long-chain alkyl group can be suitably used as the organic cation. Alkyl ammonium ions containing long chain alkyl groups include, for example, tetrabutyl ammonium ion, tetrahexyl ammonium ion, dihexyl dimethyl ammonium ion, dioctyl dimethyl ammonium ion, hexatrimethyl ammonium ion, octatrimethyl ammonium ion, dodecyl trimethyl ammonium ion, hexa Decyltrimethylammonium ion, octadecyltrimethylammonium ion, dioctadecyldimethylammonium ion, dococenyltrimethylammonium ion, hexadecylammonium ion, tetradecyldimethylbenzylammonium ion, octadecyldimethylbenzylammonium ion, dioleyldimethylammonium ion, polyoxyethylene Dode Or the like can be used monomethyl ammonium ions.

  The cation exchange capacity (CEC) of the inorganic layered compound is not particularly limited, but is preferably, for example, 25 to 200 meq / 100 g, more preferably 50 to 150 meq / 100 g, and 90 to 130 meq / More preferably, it is 100 g. If the cation exchange capacity of the inorganic layered compound is less than 25 meq / 100 g, the amount of the cationic substance inserted (intercalated) between the layers of the inorganic layered compound by ion exchange is reduced, so that the layer is sufficiently hydrophilic. May not be converted. On the other hand, when the cation exchange capacity exceeds 200 meq / 100 g, the bonding force between the layers of the inorganic layered compound becomes too strong, and the crystal flakes are difficult to peel off and the dispersibility may deteriorate.

  Specific examples of the inorganic layered compound may include products such as Kunimine Industries 'Smecton SA, Kunimine Industries' Kunipia F, Co-op Chemical's Somasif ME-100, and Co-op Chemical's Lucentite SWN.

  As a method for ion exchange (organophilicity) of an inorganic cation existing between layers of the inorganic layered compound with an organic cation, a wet method can be generally used. In the wet method, the inorganic layered compound is sufficiently solvated with water, alcohol or the like, and then an organic cation is added and stirred to replace the metal ions existing between the layers of the inorganic layered compound with the organic cation. In this method, the organic cation is sufficiently washed, filtered and dried. In addition, the inorganic layered compound and the organic cation can be directly reacted in an organic solvent, or the inorganic layered compound and the organic cation can be reacted by heating and kneading in an extruder in the presence of a resin or the like.

  The blending ratio of the inorganic layered compound and the resin having a Tg of 100 to 400 ° C. is preferably 1/100 to 100/20, more preferably 5/100 to 100/50, by mass ratio. If the blending amount of the inorganic layered compound is less than 1 part by mass with respect to 100 parts by mass of the resin having a Tg of 100 to 400 ° C., sufficient heat resistance and gas barrier properties may not be obtained. On the other hand, when the blending amount of the resin having a Tg of 100 to 400 ° C. is less than 20 parts by mass with respect to 100 parts by mass of the inorganic layered compound, brittleness and the like may be deteriorated.

  When forming a layer in which the inorganic layered compound is contained in the resin having a Tg of 100 to 400 ° C., the inorganic layered compound and the resin having a Tg of 100 to 400 ° C. are first melt-kneaded or mixed in a solution to form an inorganic layered layer. It is preferable to prepare a resin composition dispersed in a resin with the compound cleaved. Considering the production process and cost, it is preferable to mix by a melt kneading method.

  Examples of the melt kneader that can be used in the melt kneading include kneaders that are generally used for thermoplastic resins. For example, a single-screw or multi-screw kneading extruder, a roll, a Banbury mixer, or the like can be used.

  The resin composition can then be formed into a film by the usual melt extrusion method, calendar method, solution casting method and the like. Furthermore, the obtained film can be uniaxially stretched or biaxially stretched.

  The surface of the obtained layer may be subjected to corona treatment, glow treatment, UV treatment, plasma treatment or the like for the purpose of improving the adhesion with the gas barrier coat layer. Further, an anchor layer may be provided on the film surface.

  In this invention, it is preferable that the thickness of a base film is 5-500 micrometers, It is more preferable that it is 5-200 micrometers, It is further more preferable that it is 10-100 micrometers. If the base film is thin, the strength is insufficient and handling becomes difficult. If the base film is thick, the transparency and flexibility tend to be impaired.

  The gas barrier laminate film of the present invention can further have the following various functional layers in addition to the above-described inorganic layer and polysilsesquioxane-containing layer (defect filling layer).

<Transparent conductive layer>
As the transparent conductive layer, a known metal film or metal oxide film can be applied. Among these, a metal oxide film is preferable from the viewpoint of transparency, conductivity, and mechanical properties. For example, a metal oxide film such as indium oxide, cadmium oxide and tin oxide to which tin, tellurium, cadmium, molybdenum, tungsten, fluorine or the like is added as an impurity, and zinc oxide or titanium oxide to which aluminum is added as an impurity can be given. Among them, an indium oxide (ITO) thin film containing 2 to 15% by mass of tin oxide is excellent in terms of transparency and conductivity, and is preferably used. Examples of the method for forming the transparent conductive layer include methods such as vacuum deposition, sputtering, and ion beam sputtering.

  The film thickness of the transparent conductive layer is suitably 15 to 300 nm, preferably 20 to 250 nm, more preferably 30 to 200 nm. If the film thickness is 15 to 300 nm, a continuous film is obtained, sufficient conductivity is obtained, and good transparency and bending resistance are obtained.

  The transparent conductive layer may be formed on the base film side or the gas barrier coat layer side as long as it is the outermost layer, but may be formed on the gas barrier coat layer side in order to prevent the entry of a trace amount of moisture contained in the base film. preferable.

  The gas barrier laminate film of the present invention can have a known primer layer or inorganic thin film layer between the base film and the gas barrier coat layer. As the primer layer, for example, an acrylic resin, an epoxy resin, a urethane resin, a silicone resin, or the like can be used. In the present invention, an organic-inorganic hybrid layer is used as the primer layer, and an inorganic vapor deposition layer or an inorganic thin film layer is used. A dense inorganic coating thin film by a sol-gel method is preferred. As an inorganic vapor deposition layer, vapor deposition layers, such as a silica, a zirconia, an alumina, are preferable. The inorganic vapor deposition layer can be formed by a vacuum vapor deposition method, a sputtering method, or the like.

  Various functional layers may be provided on the upper or outermost layer of the gas barrier coat layer. Examples of such functional layers include optical functional layers such as antireflection layers, polarizing layers, color filters, ultraviolet absorbing layers, light extraction efficiency improving layers, mechanical functional layers such as hard coat layers and stress relaxation layers, and antistatic Examples thereof include an electrical functional layer such as a layer / conductive layer, an antifogging layer, an antifouling layer, and a printing layer.

  Further, on the gas barrier coat layer, an inorganic layer, and then an inorganic layer obtained by the sol-gel method or a layer containing polysilsesquioxane (defect filling layer) may be repeatedly laminated one or more times.

The gas barrier laminate film of the present invention has the above-mentioned base film, inorganic layer and layer containing polysilsesquioxane (defect filling layer). Therefore, the gas barrier laminate film of the present invention has an oxygen permeability of 0 to 0.01 ml / m ² · day · atm at 38 ° C. and 90% relative humidity, preferably 0 to 0.008 ml / m ^2. · Day · atm, more preferably 0 to 0.005 ml / m ² · day · atm. It is preferable that the oxygen permeability at 38 ° C. and relative humidity 90% is 0.01 ml / m ² · day · atm or less because, for example, when used in an organic EL light emitting device, the deterioration can be prevented.

The gas barrier laminate film of the present invention has a water vapor transmission rate of 0 to 0.01 g / m ² · day, preferably 0 to 0.008 g / m ² · day, at 38 ° C. and a relative humidity of 90%. Yes, and more preferably 0 to 0.005 g / m ² · day. It is preferable that the oxygen permeability at 38 ° C. and relative humidity 90% is 0.01 g / m ² · day or less because deterioration can be prevented when used in an organic EL light emitting device, for example.

[Image display element]
Although the use of the gas barrier laminate film of the present invention is not particularly limited, it can be suitably used as a transparent electrode substrate of an image display element because it is excellent in optical characteristics and mechanical characteristics.
The term “image display element” as used herein means a circularly polarizing plate / liquid crystal display element, a touch panel, an organic EL element, or the like.

<Circularly polarizing plate>
A circularly polarizing plate can be produced by laminating a λ / 4 plate and a polarizing plate on the gas barrier laminate film of the present invention. In this case, the lamination is performed so that the slow axis of the λ / 4 plate and the absorption axis of the polarizing plate are 45 °. As such a polarizing plate, it is preferable to use what is extended | stretched in the 45 degree direction with respect to the longitudinal direction (MD), For example, what is described in Unexamined-Japanese-Patent No. 2002-865554 can be used suitably.

<Liquid crystal display element>
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The gas barrier laminate film of the present invention can be used as the transparent electrode and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

  The transmissive liquid crystal display device includes a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization in order from the bottom. It has a structure consisting of a film. Among these, the gas barrier laminate film of the present invention can be used as the upper transparent electrode and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

  The liquid crystal cell is not particularly limited, but more preferably TN (Twisted Nematic) type, STN (Supper Twisted Nematic) type or HAN (Hybrid Aligned Nematic) type, VA (Vertically Alignment) type, ECB type (Electrically Controlled Birefringence), OCB A type (Optically Compensatory Bend) and a CPA type (Continuous Pinwheel Alignment) are preferable.

<Touch panel>
The touch panel can be applied to those described in JP-A-5-127822, JP-A-2002-48913, and the like.

<Organic EL device>
When the gas barrier laminate film of the present invention is used for organic EL or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP-A-2001-192653. JP, JP 2001-335776, JP 2001-247859, JP 2001-181616, JP 2001-181617, JP 2002-181816, JP 2002-181617, JP 2002-056776. It is preferable to use in combination with the contents described in each of the above publications and JP-A-2001-148291, JP-A-2001-221916, and JP-A-2001-231443.
That is, the gas barrier laminate film of the present invention can be used as a base film and / or a protective film when forming an organic EL element.

  EXAMPLES Hereinafter, although the gas barrier laminated film of the present invention will be described in detail based on examples, the present invention is not limited to these examples.

(Example 1)
1. Preparation of Resin Layer (Support ) 10 parts by mass of Somasif MTE (Corp Chemical Co., Ltd. synthetic mica) was mixed per 100 parts by mass of ZEONOR 1600R (Tg 163 ° C., cycloolefin polymer manufactured by Nippon Zeon Co., Ltd.) resin. Then, the film 1A with a film thickness of 200 μm was obtained by kneading and extruding at 270 ° C. using a twin screw extruder (Rheomix 600P / PTW25; manufactured by Haake, Germany). In addition, the resin layer which does not use Somasif MTE was produced, and this was made into the film 1B.
The light transmittance at 550 nm of the films 1A and 1B was 90% and 93%, respectively.

2. Production of First Inorganic Layer On the above films 1A and 1B, a silicon oxide layer having a thickness of 60 nm was formed by reactive deposition under vacuum while controlling the amount of Si evaporation and the amount of oxygen gas introduced. This was designated as films 2A and 2B.

3. Preparation of polysilsesquioxane- containing layer (defect filling layer) (saddle-type polysilsesquioxane)
9 g of “polycyclopentylsilsesquioxane (methacryloxy substituted) polymerizable T8 cube (manufactured by Azumax: SST-H8C51)” as a cage-type polysilsesquioxane having a polymerizable functional group, KAYARAD-DPHA as a photopolymerizable binder 1 g of (dipentaerythritol hexaacrylate) and 0.1 g of IRGACURE907 as a photopolymerization initiator were dissolved in 190 g of methyl ethyl ketone to obtain a coating solution. This coating solution was applied to the film 2A using a wire bar, and a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge with an oxygen concentration of 0.1% or less, A film 3A on which a defect compensation layer having a thickness of 100 nm was formed by irradiation with ultraviolet rays having an illuminance of 350 mW / cm ² and an irradiation amount of 500 mJ / cm ² and heating at 120 ° C. for 1 minute was obtained. Similarly, a defect filling layer was formed on the film 2B to obtain a film 3B.

(Amorphous polysilsesquioxane)
10 g of “polymethylsilsesquioxane 100% methyl (manufactured by Amax: SST-3M01)” as amorphous polysilsesquioxane and 0.05 g of didibutyltin diacetate as a curing catalyst were dissolved in 190 g of methyl ethyl ketone to obtain a coating solution. . This coating solution was applied onto the film 2A using a wire bar and heated at 120 ° C. for 1 hour to form a defect-compensating layer having a thickness of 100 nm, thereby obtaining a film 3C.

4). Production of Second Inorganic Layer On the films 3A, 3B and 3C described above, a silicon oxide layer having a thickness of 60 nm was formed by reactive deposition under vacuum while controlling the amount of Si evaporation and the amount of oxygen gas introduced. These were designated as films 4A, 4B, and 4C, respectively.

5). Production of Transparent Conductive Layer The films 4A, 4B and 4C were introduced into a vacuum chamber, and a transparent electrode made of an ITO thin film having a thickness of 200 nm was formed by DC magnetron sputtering using an ITO target. This was made into film 5A, 5B, and 5C.
Moreover, the transparent conductive layer was similarly formed in the film 3A as a sample which does not contain a 2nd inorganic layer. This was designated as film 5D.

6). Film 6A was prepared in the same manner as described above except that the defect-compensating layer of the sample-producing film 5A containing no polysilsesquioxane-containing layer (defect-compensating layer) was not prepared.

7). Preparation of a sample having a layer not containing polysilsesquioxane Other than using the following coating liquid for comparison which does not contain polysilsesquioxane, instead of the coating liquid used in the preparation of the defect compensation layer of film 5A Produced a film 7A by the same method as described above.
The comparison coating solution was 10 g of KAYARAD-DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate: manufactured by Nippon Kayaku) as a photopolymerizable binder, and 0.1 g of IRGACURE907 (manufactured by Ciba Geigy) as a photopolymerization initiator. Was dissolved in 190 g of methyl ethyl ketone.

8). Preparation of sample having only a layer containing polysilsesquioxane (defect filling layer) A film 8A in which only a defect filling layer containing a cage polysilsesquioxane was laminated on a film 1A was produced.

<Test Example 1>
Measurement of gas barrier properties Oxygen transmission rate and water vapor transmission rate of films 5A to 5D of the present invention and comparative films 2A, 2B, 6A, 7A and 8A were 38 ° C, relative humidity 10% and 90%, MOCON method (oxygen: MOCON OX-TRAN 2 / 20L, water vapor: MOCON PERMATRAN-W3 / 31). The results are shown in Table 1.

<Test Example 2>
Bending test The film sample was cut into 20 cm x 30 cm, both ends were bonded to form a cylinder with the gas barrier coat layer on the outside, and then the film and the roller with two 12 mmφ transfer rollers applied with a tension of about 1 N between the two rollers. The film was rotated and conveyed at 30 cm / min with care that the parts were in complete contact and the film did not slip. The sample was conditioned for 8 hours in an environment of 25 ° C. and a relative humidity of 60%, and the test was performed in a laboratory under the same conditions. After the above operation, gas barrier properties were measured. The results are shown in Table 2.

<Test Example 3>
Heat resistance test The surface of the barrier coating layer of the film sample was irradiated with a commercially available infrared heater until heated to a surface temperature of 250 ° C. and then allowed to cool to 25 ° C., and the gas barrier property was measured. The surface temperature was monitored with a commercially available radiation thermometer. The results are shown in Table 3.

  From Table 1, the gas barrier laminate film (films 5A, 5B, 5C, 5D) containing polysilsesquioxane in the layer containing polysilsesquioxane (defect filling layer) has only one inorganic layer. In the case (films 2A and 2B), when two inorganic layers are laminated, but there is no layer containing polysilsesquioxane (film 6A), when there is a layer not containing polysilsesquioxane ( It can be seen that the oxygen transmission rate and the water vapor transmission rate are far superior to those of the case having only the film 7A) and the inorganic defect layer (film 8A). Further, among the gas barrier laminated films of the present invention, the film (film 2A) in which the base film contains an inorganic layered compound has a significantly improved water vapor transmission rate than the film not containing the inorganic layered compound (film 2B). I understand. From this, it can be seen that the gas barrier laminated film of the present invention can provide good gas barrier performance due to the synergistic effect of laminating the inorganic layer and the defect compensation layer containing polysilsesquioxane.

  Furthermore, the films 5A, 5B, and 5D of the present invention did not deteriorate in gas barrier performance by a bending test and a heat resistance test. Further, the film 5C of the present invention was slightly deteriorated in the bending test, but it was a level having almost no influence. On the other hand, the comparative sample 6A in which the two inorganic layers were laminated but did not have the defect compensation layer had poor flexibility, and the gas barrier performance was deteriorated by the bending test. Moreover, although the comparative film 7A having a layer not containing polysilsesquioxane was superior to the above-described comparative film 6A, the heat resistance was inferior to that of the present invention, and the gas barrier performance was deteriorated by the heat resistance test. From this, it can be seen that the gas barrier laminate film of the present invention has good bending resistance and heat resistance due to the synergistic effect of laminating the inorganic layer and the layer containing polysilsesquioxane.

(Example 2)
1. The lead wire of aluminum was connected from the transparent electrode (ITO) of the board | substrate and the organic EL element production film 5A, and the laminated structure was formed.
The surface of the transparent electrode was spin-coated with an aqueous dispersion of polyethylene dioxythiophene / polystyrene sulfonic acid (BAYER, Baytron P: solid content 1.3% by mass), and then vacuum-dried at 150 ° C. for 2 hours to obtain a thickness of 100 nm. The hole transportable organic thin film layer was formed. This was designated as substrate X.

On the other hand, a coating solution for a light-emitting organic thin film layer having the following composition was formed on one side of a temporary support made of polyethersulfone (Sumitomo Bakelite Co., Ltd. Sumilite FS-1300) having a thickness of 188 μm using a spin coater. The luminescent organic thin film layer having a thickness of 13 nm was formed on the temporary support by applying and drying at room temperature. This was designated as transfer material Y.
Polyvinylcarbazole 40 parts by mass (Mw = 63000, manufactured by Aldrich)
Tris (2-phenylpyridine) iridium complex 1 part by mass (orthometalated complex)
1,200 parts by mass of 1,2-dichloroethane

  The light-emitting organic thin film layer side of the transfer material Y is superimposed on the upper surface of the organic thin film layer of the substrate X, and heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, and a temporary support Was peeled off to form a light-emitting organic thin film layer on the upper surface of the substrate X. This was designated as substrate XY.

A patterned mask (a mask with a light emission area of 5 mm × 5 mm) is placed on one side of a polyimide film (UPILEX-50S, manufactured by Ube Industries) with a thickness of 50 μm cut into 25 mm square, and Al is deposited to a thickness of 250 nm by vapor deposition. Then, LiF was formed to a thickness of 3 nm by a vapor deposition method. A coating solution for an electron transporting organic thin film layer having the following composition is applied onto the obtained laminated structure using a spin coater coating machine, and vacuum dried at 80 ° C. for 2 hours, whereby an electron having a thickness of 15 nm is obtained. A transportable organic thin film layer was formed on LiF. Furthermore, an aluminum lead wire was connected from the Al electrode, and this was used as a substrate Z.
Polyvinyl butyral 2000L 10 parts by mass (Mw = 2000, manufactured by Denki Kagaku Kogyo Co., Ltd.)
1-butanol: 3500 parts by mass An electron transporting compound having the following structure: 20 parts by mass

  Using the substrates XY and Z, the electrodes are stacked so that the electrodes face each other with the light-emitting organic thin film layer interposed therebetween, and heated and pressurized at 160 ° C., 0.3 MPa, 0.05 m / min using a pair of heat rollers, The organic EL element 1 was produced by bonding.

  Further, as a comparative organic EL element, an organic EL element 2 was prepared in the same manner as in the production of the substrate X, except that the comparative film 7A was used instead of the film 5A as a support.

A direct measure voltage was applied to the obtained organic EL elements 1 and 2 using a source measure unit 2400 type (manufactured by Toyo Technica Co., Ltd.) to emit light. The organic EL device 1 of the present invention emitted light well. The comparative organic EL element 2 emitted light relatively well.
When the organic EL elements 1 and 2 were left to stand for 10 hours at 25 ° C. and 10% and 90% relative humidity for 10 hours respectively after the element was made to emit light in the same manner, the organic EL element 1 similarly emitted good light. Although seen, in the organic EL element 2, defects increased.

  Since the gas barrier laminate film of the present invention is excellent in bending resistance, heat resistance and gas barrier properties, it can be used as a substrate for various devices, particularly image display elements. Furthermore, since the image display element of the present invention has excellent bending resistance, heat resistance and gas barrier properties, it can be used in various device products as an element having a flexible substrate.

Claims (7)

A gas barrier laminate film having at least one inorganic layer and at least one layer containing polysilsesquioxane on a base film. The gas barrier laminate film according to claim 1, wherein the inorganic layer and the layer containing the polysilsesquioxane are laminated in this order on the base film. The gas barrier laminate film according to claim 1 or 2, wherein the polysilsesquioxane is a cage polysilsesquioxane or a partially cleaved structure thereof. The gas barrier according to any one of claims 1 to 3, wherein the layer containing polysilsesquioxane is a layer containing a copolymer of polysilsesquioxane having a polymerizable functional group and a polyfunctional monomer. Laminated film. The gas barrier laminate film according to any one of claims 1 to 4, wherein the base film contains an inorganic layered compound. The oxygen permeability at 38 ° C. and 90% relative humidity is 0.01 ml / m ² · day · atm or less, and the water vapor permeability at 38 ° C. and 90% relative humidity is 0.01 g / m ² · day or less. The gas barrier laminate film according to claim 1, wherein: The image display element using the gas-barrier laminated film as described in any one of Claims 1-6.